1993 Volume 1993 Issue 9 Pages 1077-1084
The thermal polymerization of dihydrohydroxy-exo-dicyclopentadienyl and tetrahydrohydroxyexo-dicyclopentadienyl maleates was carried out at 220 °C in the absence of any initiator to investigate quantitatively the mechanism of polymer formation. The characteristics of the thermal polymerization were discussed mainly with regared to the average molecular weight, molecular weight distribution, and spectra of the products before and after hydrolysis. It seems that the presence of a double bond within the skeleton of dicyclopentadiene is necessary for the thermal polymerization to occur. This thermal polymerization is initiated by both radical chain reaction of the isomerized fumaroyl double bond and ene-reaction of the fumaroyl double bond with the allylic double bond in the cyclopentene ring. The radical chain reaction terminated rapidly at a degree of polymerization less than 6. On the other hand, the ene-reaction trends to progress with increasing molecular weight of the polymer produced.
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